CN104487161A - Filtration article with fluoropolymer knit - Google Patents

Filtration article with fluoropolymer knit Download PDF

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Publication number
CN104487161A
CN104487161A CN201380039106.6A CN201380039106A CN104487161A CN 104487161 A CN104487161 A CN 104487161A CN 201380039106 A CN201380039106 A CN 201380039106A CN 104487161 A CN104487161 A CN 104487161A
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CN
China
Prior art keywords
layer
interlocking
interlocking limit
filtration
fluorine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201380039106.6A
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Chinese (zh)
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CN104487161B (en
Inventor
E·K·普罗斯特
S·H·斯佩克
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Entegris Inc
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WL Gore and Associates Inc
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Filing date
Publication date
Priority claimed from US13/947,733 external-priority patent/US10350529B2/en
Application filed by WL Gore and Associates Inc filed Critical WL Gore and Associates Inc
Publication of CN104487161A publication Critical patent/CN104487161A/en
Application granted granted Critical
Publication of CN104487161B publication Critical patent/CN104487161B/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/36—Polytetrafluoroethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D36/00—Filter circuits or combinations of filters with other separating devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/08—Filter cloth, i.e. woven, knitted or interlaced material
    • B01D39/083—Filter cloth, i.e. woven, knitted or interlaced material of organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1692—Other shaped material, e.g. perforated or porous sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
    • D04B1/16—Other fabrics or articles characterised primarily by the use of particular thread materials synthetic threads
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B21/14—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes
    • D04B21/16—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes incorporating synthetic threads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/14—Ageing features
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/04—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons
    • D10B2321/042—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons polymers of fluorinated hydrocarbons, e.g. polytetrafluoroethene [PTFE]
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D10B2505/04—Filters

Abstract

Disclosed is a filtration article comprising a first layer comprising porous PTFE for fluid filtration (e.g., a PTFE membrane), and a second layer comprising strands of fluoropolymer fibers arranged to form a stable knit. The knit layer comprises interlocking regions that are each defined by corresponding sets of at least two interlocking loop portions of the fluoropolymer fiber strands. In filtration article embodiments, the fluoropolymer fiber strands may be twisted and/or have a rounded outer configuration. The knit layer provides improved dimensional stability as a support layer for the filtration layer and/or as a drainage layer.

Description

With the filtration article of fluoropolymer knitted fabric
Related application
This application claims the U.S. utility application No.13/947 of protection in the unexamined of submission on July 22nd, 2013; the priority of 733; and U.S. utility application No.13/947; the 733 claimed U.S. Provisional Patent Application No.61/674 submitted on July 23rd, 2012; the priority of 677; the application is the claimed U.S. utility application No.13/923 submitted on June 21st, 2013 also; the priority of 810; and U.S. utility application No.13/923; the 810 claimed U.S. Provisional Patent Application No.61/662 submitted on June 21st, 2012, the priority of 775.
Background technology
Porous film is used for widely from the filtering flow particulate of pharmacy, microelectronics, chemistry and food industry, ion, microorganism and other pollutant.In use, the film device (such as, can be contained in the fold cylinder in capsule, hollow tube, square position stacking etc.) that is formed to place in fluid stream to be filtered.
In order to meet chemically with temperature tolerance requirement, the most of filter used in semiconductor fabrication is made up of fluorinated polymer material completely.More the trend of narrow linewidth controls to bring more and more heavier burden to particle contamination in semiconductor manufacturing in semiconductor fabrication.This trend causes introducing the fluoropolymer filtration membrane with the specified pore size being low to moderate 10nm.
Although these films provide excellent particulate filter, still need the life cycle or the service time that extend film, maintain its filter efficiency simultaneously.In this regard, in typical filtering embodiment, supporting course can be positioned fluoropolymer filtration membrane downstream and resist fluid flow pressure with tread support membrane.In addition, supporting course or another downstream layer may provide drainage function (such as, by serving as the wall passed for downstream passages, so that fluid passes through liquid film flow).In this regard, also upstream drainage layer can be utilized.
In this arrangement, known upstream and downstream layer is made up of the fluorine-contained polymerisate fibre material (such as, PTFE, PFA or PVDF) in braiding, non-woven or web form.In the course of time, this braiding, non-woven or lamina reticularis may show the degree of the supporting desired by fluid pressure that fiber being moved in Rotating fields makes these layers opposing can not be provided to apply to filtration membrane.This may cause film microstructure damage and filter efficiency and drainage function to be downgraded to the degree needing to replace filter.It will be appreciated that filter is replaced not only need system-down but also extra filter cost may be caused and utilize attendant's resource.
Therefore, need a kind of filtering flow goods, it has the advantage that extends working time, and provides gratifying filter efficiency in the life-extending period of this device simultaneously.The filtering flow goods utilizing woven materials of the present invention to form meet these needs.
Summary of the invention
On the one hand, a kind of filtration article for the improvement from fluid stream filtered particles is provided, it comprises: ground floor and the second layer that can cross fluid stream location, and wherein ground floor comprises for from the porous PTFE of fluid stream filtered particles and the second layer comprises the fluorine-contained polymerisate fibre stock being arranged to form stabilization needle fabric.The second layer can provide at least one in supporting and drainage to ground floor.
More particularly, knitting fluorine-contained polymerisate fibre layer can comprise multiple interlocking limit, and each interlocking limit is limited by corresponding difference group at least two interlocking ring portions of multiply fluorine-contained polymerisate fibre.The interlocking limit of knitted fabric can limit multiple wale and multiple row, wherein at least Part I of multiply fluorine-contained polymerisate fibre, per share fluorine-contained polymerisate fibre comprises different ring portions, and different ring portions partly limits in interlocking limit and replaces interlocking limit along the difference of at least two different wale location.
About in this respect, present inventor recognizes and combinationally uses the filtration article that porous PTFE filter course and knitting fluorine-contained polymerisate fibre layer obtain having the life cycle of improvement, provides highly effective particle to filter simultaneously.More particularly, present inventor recognizes and utilizes the knitting fluorine-contained polymerisate fibre layer of the fiber strand with band interlocking ring portion to provide the dimensional stability of enhancing in the time extended, thus is convenient to the advantage that realizes mentioning.
In the embodiment be susceptible to, porous PTFE filters has the bubbling point being greater than about 30psi, measures like that as described below.Such as, in fine particle filter application, porous PTFE filter course can have the bubbling point being greater than about 50psi, and is preferably more than the bubbling point (such as, in semiconductor fabrication applications) of about 80psi.
In some embodiments, can provide the filtration article of improvement, to make in multiple interlocking limit in each cross section, the corresponding interlocking ring portion of different length is positioned at least three different levels.Can recognize, such an arrangement improves the bending fluid flowing of stability simultaneous adaptation around fiber strand in interlocking limit of knitted fabric.
For in interlocking limit each, the fiber strand of knitted layer can be provided to make corresponding interlocking ring portion extend the radian of at least 90 ° along different corresponding bow-shaped route.In some embodiments, can provide from each corresponding interlocking ring portion in interlocking limit at least partially with the radian extending at least 180 ° along different corresponding bow-shaped route.In certain embodiments, the interlocking ring portion corresponding at least partially with interlocking limit can be provided as closed hoop at least partially.
On the other hand, can provide the filtration article of improvement make in multiple interlocking limit each by fluorine-contained polymerisate fibre stock corresponding difference group at least three interlocking ring portions limit.This scheme can be used for the dimensional stability be further enhanced.
In various embodiments, the fluorine-contained polymerisate fibre stock utilized in knitted layer can be set to have various feature.Such as, fluorine-contained polymerisate fibre whole or rounding exterior arrangement can be had at least partially and/or can be twisting.In some embodiments, fluorine-contained polymerisate fibre stock can comprise monofilament or multifilament.In addition, in some applications, fluorine-contained polymerisate fibre stock can comprise macaroni yarn.
Should recognize that the knitted layer of the filtration article of improvement can be warp-knitting type.For a main example, La Sheer knitted fabric can be adopted, through compiling (Tricot) knitted fabric or other is similar knitting.
In this regard and as noted, for at least Part I of the multiply fluorine-contained polymerisate fibre utilized in knitted layer, per share fluorine-contained polymerisate fibre can comprise different ring portion, and the difference along the different wale location of at least two in multiple wale that different ring portion partly limits interlocking limit replaces interlocking limit.In other words, for at least Part I of fluorine-contained polymerisate fibre stock, per share fluorine-contained polymerisate fibre can replace between interlocking limit in the difference of at least two different wale location along knitted layer of interlocking limit and replace interlocking limit place formation ring portion in "the" shape and in the difference along at least two different wale location of interlocking limit.This layout can advantageous by being positioned at the interlocking limit place of different wale and row and traversing interlocking limit distributed load and the fluid pressure load be applied on knitted layer that distributes.In addition, in certain embodiments, knitted layer can be arranged so that at least Part II of the multiply fluorine-contained polymerisate fibre of knitted layer, per share fluorine-contained polymerisate fibre comprises different ring portions, different ring portion partly limit all or substantially all in interlocking limit in multiple wale the different interlocking limits of corresponding wale location, thus realize further power load distributing.
In an additional aspect, the knitted layer of the filtration article of improvement can have space or open space, and space or open space extend fibrage and multiple interlocking limit through knitted layer.In this regard, knitted layer can be arranged so that on the every side in knitted layer opposite side, space limit corresponding area at least about 10%, thus be convenient to by it fluid flowing.In addition, knitted layer can be configured such that fluorine-contained polymerisate fibre stock (comprising the interlocking limit limited by it) limit the opposite side area of knitted layer at least about 20%, thus be convenient to the fluid drainage layer that realizes effectively being used as by knitted layer in filtration article.In some arrangements, interlocking limit can limit this area at least about 40%.
In the embodiment of the filtration article of the improvement be susceptible to, knitting fluorine-contained polymerisate fibre layer can be positioned porous PTFE layer (such as PTFE film) downstream, at least supports to provide to PTFE layer.More particularly, knitted layer can be configured to the flow pressures of supporting cellular PTFE layer opposing through it.In addition, knitted layer can serve as drainage or wall.In various layout, downstream needle tissue layer can be positioned to PTFE layer direct neighbor or there is one or more intermediate layer between which.Downstream needle tissue layer can be interconnected to PTFE layer.
Extra knitting fluorine-contained polymerisate fibre layer can be arranged at porous PTFE layer upstream to provide drainage function.Upstream needle tissue layer can be positioned to PTFE direct neighbor or there is one or more intermediate layer between which.Upstream needle tissue layer can be interconnected to PTFE layer.
In some embodiments, knitting fluorine-contained polymerisate fibre layer and porous PTFE layer respectively can have fold configuration.More particularly, this plicated layer can be positioned at least part of nest relation.In one arrangement, nested plicated layer can around axis and along axis arrangement to limit the filtration article with tubular configuration.In this regard, the fold of each layer can be configured to be arranged essentially parallel to Axis Extension.Filtration article can be positioned so that fluid stream flows to the inner space of tubular configuration outside its tubular configuration by filtration article.Alternatively, the contrary fluid flow direction by tubular configuration can be adopted.
In another characterizes, a kind of filtration article can be provided, it is positioned in fluid stream, and this filtration article of direction of flow is applied to the fluid pressure load about between 1psid and 10psid, and wherein multiple interlocking limits of knitted layer limit multiple space on knitted layer between interlocking limit.In this regard, each in space can have the second area corresponding when being positioned in fluid stream of the first surface sum before being positioned in fluid stream.Knitted layer can be arranged to in multiple space for each, and corresponding second area is less than its first corresponding area about two times.
On the other hand, a kind of filtration article can be provided, it is positioned in fluid stream, this filtration article of direction of flow is applied to the fluid pressure load about between 1psid and 10psid, wherein knitted layer be configured to each in its interlocking limit be positioned the corresponding distance of adjacent interlocking limit in multiple interlocking limit along the wale of knitted layer with row.And for each in multiple interlocking limit, the distance corresponding when knitted layer is positioned in fluid stream can initial value before it is positioned in fluid stream 200% in.
On the other hand, a kind of method from the filtering flow particle fluid stream is provided.The method can comprise the following steps: utilize the porous PTFE film crossing fluid stream location to come from fluid stream filtered particles.The method also can comprise: the stabilization needle tissue layer of utilization with porous PTFE film adjacent positioned and in porous PTFE film downstream, supporting cellular PTFE film resists the fluid pressure load applied by fluid stream.
The stabilization needle tissue layer adopted in the method comprises multiply fluorine-contained polymerisate fibre, multiply fluorine-contained polymerisate fibre is arranged to form knitted fabric, knitted fabric has multiple interlocking limit, and multiple interlocking limit is respectively limited by corresponding difference group at least three interlocking ring portions of multiply fluoropolymer.At this, the method can be included on knitted layer at interlocking limit punishment cloth fluid pressure load.
By considering that embodiment provided below describes, many additional features of the present invention and advantage obvious for those skilled in the art.
Accompanying drawing explanation
Fig. 1 shows the embodiment of the filter comprising filtration article embodiment of the present invention,
Fig. 2 A and Fig. 2 B shows the embodiment of the knitted layer of filtration article embodiment of the present invention,
Fig. 3 A and Fig. 3 B is the image of the knitted layer embodiment of filtration article of the present invention.
Fig. 4 A shows the knitted construction of another knitted layer embodiment shown in Fig. 4 B.
Detailed description of the invention
Be described herein the embodiment of the filtering flow goods comprising at least one deck fluoropolymer woven materials.Knitted layer can be used as supporting course and/or fluid drainage layer in filtration cartridges, and filter cylinder can be made up of fluorinated polymer material completely.(multiple) knitted layer like this provides the quality and the filtration article of gratifying particle filtration efficiency service time with improvement.
Fig. 1 shows filter cylinder (100), it can be made up of fluorinated polymer material completely and size can be applicable to being positioned in capsule filter (102) (describing with dotted line in FIG), and fluid stream (FS) is flowed by capsule filter.Filter cylinder (100) can comprise filtration article (1), and filtration article (1) comprising: fold porous fluoropolymer polymer filtration film (10), be placed in the fold fluoropolymer knitted layer (12) on the downstream of filtration membrane (10) and be placed in the optional fold fluoropolymer knitted layer (14) on the upstream side of filtration membrane (10).As shown in the figure, filtration membrane (10), knitted layer (12) can be nested at least in part with knitted layer (14).The one or both ends of the corrugated filter film (10) of filtration article (1), knitted layer (12) and knitted layer (14) can be packed to make these ends sealably interconnect.
It should be understood that in filtration article, utilize fold to configure adds filtration capacity by adding the operational size of filtration membrane (10).In the embodiment shown in fig. 1, corrugated filter goods (1) are cylindrical, tubular configuration, it has the fold outstanding being toward the outside inverted V-arrangement configuration, and these folds around the longitudinal axis location of filtration article (1) and along the longitudinal axis extend from one end of filtration article (1) to the other end.In this regard, fold around and between adjacent pleats in fold of the longitudinal axis of goods, limit V-arrangement region or paddy.
Filter cylinder (100) also can comprise inner core (20), outer cage (22) and End assemblies (24), (26).End assemblies (24) can comprise: annular construction member (24a), and annular construction member (24a) has the annular interface of to interconnect with outer cage (22) (such as, operating to surface melting via surface); With enclosed member (24b), it has the annular surface (such as, operating to surface melting via surface) interconnected with annular construction member (24a).End assemblies (26) can comprise: annular construction member (26a), and it has the annular surface interconnected with the annular surface of flanged tube-like interface component (26b); And, containment member (26c) (such as, O shape ring), it is placed on tube-like interface component (26b), and wherein End assemblies (26) is sealably interconnected in the discharge port of capsule filter (102).
Fluoro-containing copolymer film (10) can comprise expanded PTFE film, it can according to such as in U.S. Patent No. 7,306,729, U.S. Patent No. 3,953,566, U.S. Patent No. 5,476,589 and U.S. Patent No. 5,183, method preparation described in 545, the mode that these patents are quoted in full is incorporated into herein.Fluoro-containing copolymer film can also comprise expanded polymeric material, expanded polymeric material comprises sense TFE copolymer material, sense TFE copolymer material comprises the micro-structural being characterized as node and being interconnected by fibrillation, and wherein sense TFE copolymer material comprises the copolymers containing hydroxyl and carboxyl groups of TFE and PSVE.Sense TFE copolymer material can according to the method preparation described in U.S. Patent Bulletin No.2010/0248324, and the mode that this bulletin is quoted in full is incorporated into herein.
Core (20), cage (22) and End assemblies (24), (26) can comprise known thermoplastic fluoropolymer such as PFA, FEP, ETFE, PCTFE, ECTFE, PVDF etc.
As shown in Figure 1, filter cylinder (100) can be positioned to flow into fluid stream (FS) in capsule filter (102) by the opening in cage (22), by filtration article 1 and by the open flow of core (20) to tubular passageway, tubular passageway extends through filter cylinder (100) and via End assemblies (26) from filter cylinder (100) out.Upstream needle tissue layer (14) serves as distance piece to provide path between the surface toward the outside of the adjacent pleats of the fold at filtration membrane (10) and through the fluid flowing on these surfaces toward the outside.Downstream layer (12) serve as distance piece with to filtration membrane (10) towards providing path through the flowing of these fluids towards interior surface between interior surface.The fluid pressure that downstream needle tissue layer (12) is positioned to opposing applying further provides supporting to filtration membrane (10).
In rear one side, in arrangement illustrated, downstream layer (12) can be positioned to filtration membrane (10) direct neighbor with the fluid pressure load providing surperficial effects on surface to support to filtration membrane (10) to resist fluid stream FS to apply.In other is arranged, downstream layer (12) can provide supporting to filtration membrane (10), and one or more intermediate layer is positioned between downstream layer (12) and filtration membrane (10).
As noted above and further describe hereinafter, downstream layer (14) can have knitted construction, knitted construction advantageously goes up distribute fluids pressure load via interlocking limit at downstream layer (14), thus obtains attribute service time of stability and the prolongation strengthened relative to existing filtering flow goods.In some layout such as all folds as shown in Figure 1 configuration, the knitted construction of downstream layer (14) also limits path between interlocking limit and around interlocking limit so that fluid is by this flow channels, i.e. film drainage function.
In various embodiments, filtration article (such as, filter article mentioned above (1)) filter course can be comprised (such as, filtration membrane mentioned above (10)) and one or more knitted layer is (such as, downstream layer mentioned above (12) and/or upstream layer (14)), knitted layer comprises fluorine-contained polymerisate fibre stock, fluorine-contained polymerisate fibre stock is arranged to limit the knitted fabric with interlocking limit, interlocking limit has interlocking ring, interlocking ring reduces material extending at least one direction to obtain the more stable knitted fabric of size.And the configuration of the interlocking ring of knitted construction provides exceptional space, with to allow in staggered fiber and around various liquid flow patterns.Compared with having the knitting structure of the orthogonal fiber being only limitted to knitted fabric aperture openings that wherein flows, this is favourable.
The fiber of (multiple) knitted layer can comprise the fluoropolymer being selected from PTFE, PVDF, FEP or PFA.Preferably, PTFE fiber may be used for constructing knitted layer.PTFE knitted layer is made up of the yarn with at least one PTFE fiber.Term PTFE represents and also comprises expansion PTFE, the expandable copolymer of expansion-modifying PTFE and PTFE, as in U.S. Patent No. 5,708,044, No.6,541,589 and No.7,531,611 and U. S. application No.11/906,877 and No.12/410, described in 050, the mode that all these patents are quoted in full is incorporated into herein.PTFE fiber comprises directed fibrillation and can be non-porous or porous.PTFE fiber can be monofilament or its can be that there is the different PTFE fiber of different Denier, density, length and difference in size two kinds.The multi-strand yarns with the fluorine-contained polymerisate fibre of other type of at least one PTFE fiber and the non-PTFE of at least one also may be used in filtration article embodiment.
Fig. 2 A and Fig. 2 B shows the embodiment of the structure of the knitted layer (50) of filtration article embodiment.Should be appreciated that, knitted layer (50) can be positioned downstream and/or the upstream of filter course, and filter course comprises porous PTFE material (such as, PTFE film) with from fluid stream filtered particles.In this regard, knitted layer (50) can provide supporting and drainage function when being positioned filter course downstream, and can provide drainage function when being positioned filter course upstream.
As shown in the embodiment at Fig. 2 A and Fig. 2 B, knitted layer (50) can comprise fluorine-contained polymerisate fibre stock (60), fluorine-contained polymerisate fibre stock (60) is arranged to limit multiple interlocking limit (70), all irises out for two in these interlocking limits in Fig. 2 A and Fig. 2 B.Knitted layer (50) shown in Fig. 2 A and Fig. 2 B shows interlocking limit (70) and is in non-tension so that understand, and should be appreciated that interlocking limit (70) is tightened up before the use (such as, as shown in the embodiment at Fig. 3 A and Fig. 3 B).As shown in the figure, each in interlocking limit (70) is respectively limited by corresponding difference group at least two interlockings ring portion (62) of stock (60).Interlocking limit (70) can limit multiple wale (80) and multiple row (82).
Interlocking limit (70) can constrain in relative movement and/or the elongation of the stock (60) between interlocking limit (70) by distribute fluids pressure load between interlocking limit (70), thus the stability be improved.Thus, in the embodiment shown in Fig. 2 A and Fig. 2 B, interlocking limit (70) is respectively limited by corresponding difference group three interlockings ring portion (62) of fluorine-contained polymerisate fibre (60) stock.As shown in the figure, for a part for stock (60), per sharely comprise different ring portion, the difference that different ring portion partly limits at least two different wales location along described multiple wale (80) of multiple interlocking limit (70) replaces interlocking limit.In addition, for another part of stock (60), per sharely comprise different ring portions, different ring portions partly limits the different interlocking limits being arranged in the corresponding wale of wale (80) of all interlocking limits (70).Interlocking limit (70) is set like this by traversing interlocking limit (70) distributed load and to distribute the fluid pressure load be applied on knitted layer (50) at interlocking limit (70) place being arranged in different wale and wale.
Such as, in the embodiment of Fig. 2 A, for a part for stock (60), per sharely comprise different ring portions, the difference of two adjacent windings stringer location in wale (80) that different ring portions partly limits in multiple interlocking limit (70) replaces interlocking limit, and in the embodiment of Fig. 2 B, for a part for stock (60), per sharely comprise different ring portion, the difference being positioned with two wale location of another wale (80) in wale (80) therebetween that different ring portion partly limits in multiple interlocking limit (70) replaces interlocking limit.
In various embodiments, the ring portion of the stock (60) of restriction interlocking limit (70) can be positioned to the radian along the corresponding bow-shaped route extension about at least 90 ° of difference.With reference to the embodiment of figure 2A and Fig. 2 B, the part of the ring portion of the stock (60) corresponding from interlocking limit (70) can be positioned to the radian extending approximately at least 180 ° along different corresponding bow-shaped routes.
Fig. 3 A and Fig. 3 B shows the image of the embodiment of PTFE knitted layer (90) of the present invention.Knitted layer (90) comprises expansion PTFE (ePTFE) fiber and uses embedded La Sheer purl design (2bar in lay Raschel locked stitch design) of 2 sley bar to form.Such being configured in shown in Fig. 4 A and Fig. 4 B in the embedded La Sheer of 2 sley bar designs.Knitted layer (90) is at wale with through upwards providing the structure of dimensionally stable.
The low-friction coefficient of PTFE brings challenge to the knitted fabric constructing dimensionally stable.But, by using the interlocking suture needle design of enforcement 2 sley bar embedded interlocking suture needle, in the knitted layer shown in Fig. 2 A, Fig. 2 B, Fig. 3 A and Fig. 3 B, can the stable knitted fabric of construction size.
Although Fig. 2 A, Fig. 2 B, Fig. 3 A, Fig. 3 B, Fig. 4 A and Fig. 4 B show concrete knitting design embodiment, should be appreciated that any knit pattern that also can be used in and (multiple) wale and/or row direction obtain dimensional stability, such as using the weft-knitted fabric that interlocking suture needle designs through compiling (Tricot).
Fluoropolymer knitted fabric described herein can be positioned over upstream or the downstream of filtration membrane.Knitted layer can be positioned over the upstream and downstream of filtration membrane.Knitted layer can be set to various configurations (such as, plane, plane with fold, tubulose, tubulose with fold etc.).In one arrangement, on the opposite side that knitted layer can be positioned filtration membrane and these layers may folds and as above contemplated arrive, use known method described in the art at end part seal to form fold filter cylinder.In addition, cylinder can also be positioned in capsule or shell, and fluid flows through capsule or shell.
In various embodiments, intermediate layer can be placed between filtration membrane and knitted layer.Intermediate layer can provide additional support.Appropriate intermediate layers comprises porous fluoropolymer net, braid, film or non-woven fabric.Preferred interlayer can be the porous fluoropolymer article described in U.S. Patent Bulletin No.2012/064273.
For explanation with describe object and give and of the present inventionly to describe above.In addition, description there is no the intention limiting the invention to form disclosed herein.Therefore, corresponding with knowledge to the skill of above-mentioned instruction content and correlation technique variants and modifications within the scope of the invention.Embodiment as described above is intended to further explain known embodiments of the present invention and makes those skilled in the art can with this embodiment and other embodiment to utilize the present invention and to need to make various amendment according to application-specific of the present invention or purposes.Claims are intended to comprise the alternate embodiment in prior art allowed band.
Method of testing and measurement
Viscous liquid flowing test
By mixing 75% volume glycerine and 25% volume Dl water prepares glycerine water solution.This solution is measured as about 40cp in the viscosity of room temperature (75 ℉).Filtration article test sample (47mm diameter) is positioned in retainer securely.Glycerite is pumped through test sample, and the initial differential pressure wherein traversing test sample is about 50psid.Test sample comprises the stacking of filtration membrane and downstream needle tissue layer.Alternatively, test sample and can comprise intermediate layer and/or upstream needle tissue layer.The pressure reduction of test sample is traversed, as one or more middle in example is below reported at whole test time record.
Initial differential pressure is used as the instruction of sample strength from the 50psid time be reduced to more needed for low value.Time needed for pressure reduction reduces is longer, and sample more by force or more stable.For the sample of low-intensity, stability, pressure reduction is reduced to more low value cost from 50psid and is less than the time of 10 minutes.High strength sample usually maintains initial differential pressure 50psid and continues about at least 24 hours.
Think that the stability that this test provides fluid drainage layer to resist the applied pressure suitably ability of tread support membrane layer is measured.Also think that this test provides the correlation with the long-term particle filter efficiency of testing sample.That is, the test sample of the high strength of this test instruction also has excellent long-term particle filter efficiency.
Long-term particle filter efficiency is tested
This test is used for measuring the long-term particle filter efficiency that filtration article referred to above tests sample.Sample is positioned in corrosion resistant plate (diameter 90mm), and corrosion resistant plate makes the center to center between any two holes be 9.6mm with the hole of 19 diameter 9.6mm that are spaced apart from each other.Then sample and corrosion resistant plate are positioned over inside retainer, and retainer has fluid intake and outlet.Test process is below used to measure particle filtration efficiency and particle filtration efficiency is reported as exhibits initial filtration efficiency.
First test sample utilizes IPA moistening and uses 250mL to comprise 0.1% the Dl aqueous solution of X-100 carries out initial wash.This washing is carried out under about 3psid differential pressure of traversing test sample.Collect effluent and be labeled as " background ".
49nm microballoon (Part No. B50, Thermo Fisher Scientific Inc.) is used to prepare challenge solution.By comprising 0.1% to 2 liters the Dl aqueous solution of X-100 adds 83 microlitres and comprises 1% weight margin solution of 49nm microballoon to prepare 49nm challenge solution.
Then, under the differential pressure of traversing filtration membrane 6psid, the challenge solution of 250mL is allowed to pass through liquid film flow.Challenge solution exposes directly to fluid flowing.Collect filter liquor and be labeled as in " downstream ".
Cary Eclipse sepectrophotofluorometer is used for measuring the fluorescence intensity of challenge solution, background and downstream sample.The calibration criterion utilizing the challenge solution of three kinds of different particle concentrations of given microballoon size to generate contrasts 3 point curves to calibrate from spectrophotometric ionization meter.
From intensity level, calculate particle according to following equation and retain efficiency (E) %:
Replication filtration product sample be positioned over there is as described above design and size another corrosion resistant plate on.Then be positioned over together with corrosion resistant plate in retainer by sample, retainer has fluid intake and outlet.Sample exposes lasting 14 days to the propane diols flowing of 140 DEG C.The differential pressure of traversing sample is about 3.0psid.
After 14 days, measure the particle filtration efficiency of this sample as described above and be reported as final efficiency (after exposing 14 days to the propane diols of 140 DEG C).
Between starting efficiency number and final efficiency numbers, insignificant change shows that test specimens product provide excellent long-term particle retain and will represent that the life period at filter is maintained its particle filtration efficiency by this test sample.
Bubbling point is measured
Use (purchased from New York Ithaca (Ithaca, N.Y.) porous material company (Porous MaterialsInc.), model C FP 500AEXL), measure the bubbling point of the filtration membrane sample that can adopt in filtration article according to the general instruction content of ASTM F31 6-03.Sample thin film can be positioned in sample chamber and to utilize SilWick silicone fluid (can purchased from Porous Materials Inc.) moistening, and SilWick silicone fluid has the surface tension of 19.1dynes/cm.The bottom jaw of sample chamber has 2.54cm diameter, 3.175mm thick porous metals dish plug-in unit is (not special metallurgical, Farmington, the Connecticut State (Mott Metallurgical, Farmington, Conn.), 40 micron porous metal dishes) and the top clamp of sample chamber has 3.175mm diametric hole.Use Capwin software version 6.62.1, the parameter as specified in the following table can be set.The value provided for bubbling point is the mean value of twice test.
Parameter Set-point
Maximum stream flow (cc/m) 200000
Bubble flow (cc/m) 100
F/PT (old bubble time) 40
Minimum bubble pressure (PSI) 0
Zero-time (sec) 1
V2 increases (cts) 10
Dipping increases (cts) 1
Pulse daley (sec) 2
Maximum pressure (PSI) 500
Pulse width (sec) 0.2
The minimum equivalent time (sec) 30
Pressure conversion (cts) 10
Flow transition (cts) 50
Equivalence repeats 3
Average repetition 20
Maximum pressure diffusion (PSI) 0.1
Maximum fluidity diffusion (cc/m) 50
Initial pressure (PSI) 1
Initial flow (cc/m) 500
example 1
Utilize the expansion PTFE fiber with feature described in table 1 to prepare knitting sample.Form the warp beam comprising 400 ends of ePTFE fiber, wherein, the tension force on axial extent keeps constant, causes the warp beam with minimum wrinkle and fiber crossovers.Warp beam is positioned on typical 2-sley bar warp knitting machine.The Extra Supply cone of ePTFE fiber is for inserting fiber.The design of 2-sley bar embedded La Sheer purl is used to produce desired knitting.
Table 1
Above-mentioned knitted layer is positioned over according to U.S. Patent Bulletin No.2010/0248324 and U.S. Patent Bulletin No.2011/0039960 and U.S. Provisional Patent Application No.61/538 co-pending, the expanded PTFE film layer downstream that the instruction content of 625 manufactures.Make the stacking of these two layerings stand the test of long-term particle filter efficiency, wherein film side is exposed to direct flow flowing.Starting efficiency and final efficiency are measured as 95%, show that this stacking excellent long-term particle retains.
The stacking of these two layerings stands viscous liquid flowing test, and wherein film side is directly exposed to fluid flowing.Do not observe stacking two ends differential pressure (initial value from 50psid) even at 24 hours later to reduce.This test run 96 hours and even not do not occur after 96 hours that observable differential pressure reduces.
example 2
The intermediate layer of the coherent scramble network of the porous article that comprises and there is layer of expanded ptfe and the FEP particle on side has been manufactured according to the instruction content of U.S. Patent Bulletin No.2012/064273.This layer is positioned between the stacking expanded PTFE film of example 1 and knitted layer.This orientation makes the ePTFE layer in intermediate layer be close to knitted layer and the coherent scramble network of FEP particle is close to stacking ePTFE layer.This stacking long-term particle filter efficiency that stands is tested.Starting efficiency and final efficiency are all measured as 95%, show that this stacking excellent long-term particle retains.
comparative example 1
PTFE stratum reticulare and expanded PTFE film remove from the fold filter cylinder that can obtain from market (the production number ABFG1GPK3EH1-K3 Ultikleen G2 Excellar ER20nm from Solution (Pall Corporation)).These two layer stack stand viscous liquid flow measurement, and wherein film side is directly exposed to fluid flowing.Differential pressure was reduced to from 50psid and is less than about 5psid in 5 minutes, represented low stability.
Test according to this stacking long-term particle filter efficiency, starting efficiency and final efficiency are respectively 90% and 69% through measuring, and represent poor long-term particle retention property.
comparative example 2
PTFE stratum reticulare and expanded PTFE film from the fold filter cylinder that can obtain from market (from the production number FLHF050-10M3F-PW-300Fluoryte of PallCorporation tM50nm) remove.These two layer stack stand viscous liquid flow measurement, and wherein film side is directly exposed to fluid flowing.Differential pressure was reduced to from 50psid and is less than about 5psid [readding again] in 5 minutes.
comparative example 3
The fold filter cylinder that commercially arrives (from the product QCCYATM01 of Mike Ruo Lisi company (MykrolisCorporation), 0.03 um nominal cylinder) remove PFA braid.By the expanded PTFE film of the 0.1 um nominal pore size from commercially available fold filter cylinder ( xF SELECT, Parker Hannifin Corporation (ParkerHannifin Corporation)) be positioned over PFA braid upstream.These two layer stack stand viscous liquid flow measurement, and wherein film side is directly exposed to fluid flowing.Differential pressure was reduced to from 50psid and is less than about 5psid in 5 minutes.

Claims (41)

1., for the filtration article from fluid stream filtered particles, comprising:
Ground floor, described ground floor can cross fluid stream location, comprises for the porous PTFE film from described fluid stream filtered particles; And
The second layer, the described second layer can cross described fluid stream location to provide at least one in the drainage of described ground floor and supporting, the described second layer comprises multiply fluorine-contained polymerisate fibre, described multiply fluorine-contained polymerisate fibre is arranged to form knitted fabric, described knitted fabric has multiple interlocking limit, described multiple interlocking limit is respectively limited by corresponding difference group at least two interlocking ring portions of described multiply fluorine-contained polymerisate fibre, described multiple interlocking limit of wherein said knitted fabric limits multiple wale and multiple row, and wherein at least Part I of described multiply fluorine-contained polymerisate fibre, per share fluorine-contained polymerisate fibre comprises different ring portions, described different ring portion partly limits in described multiple interlocking limit and replaces interlocking limit along the difference of the different wale location of at least two in described multiple wale.
2. filtration article according to claim 1, is characterized in that, each region in described multiple interlocking limit is limited by corresponding difference group at least three interlocking ring portions of described multiply fluorine-contained polymerisate fibre.
3. filtration article according to claim 2, is characterized in that, for each in described multiple interlocking limit, described corresponding interlocking ring portion respectively extends the radian of at least 90 ° along different corresponding bow-shaped routes.
4. filtration article according to claim 3, is characterized in that, in described multiple interlocking limit in each cross section, the different length of described corresponding interlocking ring portion is positioned at least three different levels.
5. filtration article according to claim 4, is characterized in that, for each in described multiple interlocking limit, described corresponding interlocking ring portion respectively extends the radian of at least 180 ° along different corresponding bow-shaped routes.
6. filtration article according to claim 4, is characterized in that, in described multiple interlocking limit in each, described corresponding interlocking ring portion engages along described corresponding bow-shaped route frictionally to limit the relative movement between them.
7. filtration article according to claim 4, is characterized in that, each in described multiple interlocking limit comprises the multiple bending fluid flow path through each extends in described at least three different levels.
8. filtration article according to claim 1, is characterized in that, described multiply fluorine-contained polymerisate fibre there is rounding exterior arrangement at least partially.
9. filtration article according to claim 8, is characterized in that, the per share of at least described part of described multiply fluorine-contained polymerisate fibre is twisting.
10. filtration article according to claim 1, is characterized in that, in described multiply fluorine-contained polymerisate fibre is twisting at least partially.
11. filtration articles according to claim 1, it is characterized in that, for at least Part II of described multiply fluorine-contained polymerisate fibre, per share fluorine-contained polymerisate fibre comprises different ring portions, and described different ring portion partly limits the different interlocking limits being arranged in the corresponding wale of described multiple wale in all described multiple interlocking limits.
12. filtration articles according to claim 1, it is characterized in that, described fluid stream has at the fluid pressure load about between 1psid and 10psid, wherein said multiple interlocking limit limits multiple space on described knitted layer between described interlocking limit, each in wherein said multiple space has corresponding first surface sum before being positioned in the described fluid stream second area corresponding when being positioned in described fluid stream, and wherein for each in described multiple space, described corresponding second area is less than its corresponding the first area two times.
13. filtration articles according to claim 1, it is characterized in that, described fluid stream has at the fluid pressure load about between 1psid and 10psid, wherein said multiple interlocking limit limits multiple space on described knitted layer between described interlocking limit, each in wherein said multiple space has corresponding first surface sum before being positioned in the described fluid stream second area corresponding when being positioned in described fluid stream, and wherein for each in described multiple space, described corresponding second area is less than its corresponding the first area two times, each in wherein said multiple interlocking limit is positioned the corresponding distance of adjacent area in described multiple interlocking limit along described wale and row, and wherein for each in described multiple interlocking limit, when being positioned in described fluid stream described corresponding distance before it is positioned in described fluid stream initial value 200% in.
14. filtration articles according to claim 1, is characterized in that, the contiguous described ground floor location of the described second layer and be positioned described ground floor downstream to provide to described ground floor and at least support.
15. filtration articles according to claim 14, it is characterized in that, described ground floor and described second layer fold and be positioned at least part of nest relation, and the fold of the wherein said second layer is parallel to one of described multiple wale or described multiple row extends.
16. filtration articles according to claim 15, characterized by further comprising:
The third layer of fold, the third layer of described fold can cross the upstream that described fluid stream is positioned at described ground floor by nest relation at least partly, to provide drainage to described ground floor, and comprise multiply fluorine-contained polymerisate fibre, described multiply fluorine-contained polymerisate fibre is arranged to form knitted fabric, described knitted fabric has multiple interlocking limit, described multiple interlocking limit is respectively limited by corresponding difference group at least two interlocking ring portions of described multiply fluorine-contained polymerisate fibre, described multiple interlocking limit of wherein said knitted fabric limits multiple wale and multiple row, and wherein at least Part I of described multiply, per sharely comprise different ring portions, described different ring portion partly limits in described multiple interlocking limit and replaces interlocking limit along the difference of the different wale location of at least two in described multiple wale.
17. filtration articles according to claim 14, is characterized in that, the described second layer and described ground floor direct neighbor are located.
18. filtration articles according to claim 14, is characterized in that, described ground floor and the second layer interconnect.
19. filtration articles according to claim 14, characterized by further comprising:
Third layer, described third layer can be crossed described fluid stream and is positioned at described ground floor upstream, drainage is provided to described ground floor, described third layer comprises multiply fluorine-contained polymerisate fibre, described multiply fluorine-contained polymerisate fibre is arranged to form knitted fabric, described knitted fabric has multiple interlocking limit, described multiple interlocking limit is respectively limited by corresponding difference group at least two interlocking ring portions of described multiply fluorine-contained polymerisate fibre, described multiple interlocking limit of wherein said knitted fabric limits multiple wale and multiple row, and wherein at least Part I of described multiply, per sharely comprise different ring portions, described different ring portion partly limits in described multiple interlocking limit and replaces interlocking limit along the difference of the different wale location of at least two in described multiple wale.
20. filtration articles according to claim 19, is characterized in that, described ground floor, the second layer and third layer are interconnection.
21. filtration articles according to claim 1, is characterized in that, space extends described multiple interlocking limit through the described second layer.
22. filtration articles according to claim 21, is characterized in that, the area of the opposite side of the described second layer is limited by described knitted fabric and described space and wherein said space limits at least 10% of described area.
23. filtration articles according to claim 22, is characterized in that, described interlocking limit limits at least 40% of described area.
24. filtration articles according to claim 1, is characterized in that, described porous PTFE film has the bubbling point at least about 30psi.
25. filtration articles according to claim 1, is characterized in that, described porous PTFE film has the bubbling point at least about 50psi.
26. filtration articles according to claim 1, characterized by further comprising: be placed at least one intermediate layer between described ground floor and the described second layer.
27. filtration articles according to claim 1, is characterized in that, described fluoropolymer is selected from PTFE or PFA.
28. filtration articles according to claim 1, is characterized in that, the described multiply fluorine-contained polymerisate fibre comprising the described second layer is the fiber being arranged to be formed La Sheer knitted fabric.
29. filtration articles according to claim 1, is characterized in that, described knitted fabric is stablized at least two orthogonal directions.
30. filtration articles according to claim 1, is characterized in that, described fluorine-contained polymerisate fibre comprises and adds twisted filament.
31. filtration articles according to claim 1, is characterized in that, described fluorine-contained polymerisate fibre comprises one of monofilament and multifilament.
32. filtration articles according to claim 1, is characterized in that, described fluorine-contained polymerisate fibre comprises macaroni yarn.
33. 1 kinds of filters, described filter has filter cage and is placed in the filter element in described filter cage, described filter element comprises filtration article according to claim 1, wherein said ground floor and second layer fold and be packaged into along ground floor described at least one edge joint and the second layer.
34. 1 kinds of capsule filters, described capsule filter comprises filter according to claim 33.
35. 1 kinds, for the method from fluid stream filtered particles, comprising:
Utilize the porous PTFE film crossing fluid stream location from the fluid stream filtered particles with certain fluid pressure; And
Utilize the stabilization needle tissue layer being positioned described porous PTFE film downstream, support the fluid pressure load that the opposing of described porous PTFE film is applied by described fluid stream.
36. methods according to claim 35, it is characterized in that, described knitted layer comprises multiply fluorine-contained polymerisate fibre, described multiply fluorine-contained polymerisate fibre is arranged to form knitted fabric, described knitted fabric has multiple interlocking limit, and described multiple interlocking limit is respectively limited by corresponding difference group at least three interlocking ring portions of described multiply fluoropolymer.
37. methods according to claim 36, is characterized in that, described holding step comprises:
Traverse described knitted fabric to distribute on the described interlocking limit of described knitted fabric described fluid pressure load.
38. according to method according to claim 37, described fluid pressure load is about between 1psid and 10psid, wherein said multiple interlocking limit limits multiple space on described knitted layer between described interlocking limit, each in wherein said multiple space has corresponding first surface sum before being positioned in the described fluid stream second area corresponding when being positioned in described fluid stream, and wherein for each in described multiple space, described corresponding second area is less than its corresponding the first area two times.
39. according to method according to claim 37, it is characterized in that, described multiple interlocking limit of wherein said knitted fabric limits multiple wale and multiple row, and wherein at least Part I of described multiply fluorine-contained polymerisate fibre, per share fluorine-contained polymerisate fibre comprises different ring portions, and described different ring portion partly limits in described multiple interlocking limit and replaces interlocking limit along the difference of the different wale location of at least two in described multiple wale.
40. according to method according to claim 39, described fluid pressure load is about between 1psid and 10psid, each in wherein said multiple interlocking limit is positioned the corresponding distance of adjacent area in described multiple interlocking limit along described wale and row, and wherein for each in described multiple interlocking limit, when being positioned in described fluid stream described corresponding distance before it is positioned in described fluid stream initial value 200% in.
41., according to method according to claim 39, is characterized in that, each region in described multiple interlocking limit is limited by corresponding difference group at least three interlocking ring portions of described multiply fluorine-contained polymerisate fibre.
CN201380039106.6A 2012-07-23 2013-07-23 Filtration article with fluoropolymer knit Active CN104487161B (en)

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US13/947,733 US10350529B2 (en) 2012-06-21 2013-07-22 Filtration article with fluoropolymer knit
US13/947,733 2013-07-22
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